CN112105623A - Molecular catalyst for selective hydrogenolysis of amides - Google Patents

Molecular catalyst for selective hydrogenolysis of amides Download PDF

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CN112105623A
CN112105623A CN201980032312.1A CN201980032312A CN112105623A CN 112105623 A CN112105623 A CN 112105623A CN 201980032312 A CN201980032312 A CN 201980032312A CN 112105623 A CN112105623 A CN 112105623A
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compound
acid
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hydrogenolysis
methallyl
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CN112105623B (en
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J·克兰克迈尔
S·维斯托伊斯
W·莱特纳
R·T·亨布里
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Eastman Chemical Co
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Abstract

A compound named 1,1, 1-tris (bis (3, 5-dimethoxyphenyl) phosphinomethyl) ethane. The compounds may be represented by the structure of formula (I):

Description

Molecular catalyst for selective hydrogenolysis of amides
Technical Field
The present invention relates generally to the field of organic chemistry. It particularly relates to organic ligands, organometallic complexes containing such ligands, methods of preparation, and methods of using such ligands and complexes.
Background
Reducing amides is an important reaction in organic synthesis. However, conventional methods suffer from various disadvantages, such as the production of large amounts of waste/by-products and/or the requirement for harsh conditions.
Accordingly, there is a need in the art to provide alternative and/or improved methods for hydrogenolysis of amides to form amines and optionally alcohols.
This need and other needs are addressed by the present invention, which will become apparent from the following description and appended claims.
Disclosure of Invention
The invention is as set forth in the appended claims.
Briefly, in one aspect, the present invention provides a compound having the structural formula (I):
Figure 125927DEST_PATH_IMAGE001
。
in another aspect, the present invention provides an organometallic compound having the structural formula (II):
Figure 511909DEST_PATH_IMAGE002
wherein Ar represents a 3, 5-dimethoxyphenyl group and L represents a leaving group.
In yet another aspect, the present invention provides a method for hydrogenolysis of an amide. The method comprises the following steps:
contacting the amide with hydrogen in the presence of an organometallic catalyst comprising a central metal and a tridentate ligand under conditions effective to form an amine and optionally an alcohol,
wherein the central metal comprises ruthenium, and
wherein the tridentate ligand has structural formula (I).
Drawings
Figure 1 is a graph of hydrogen pressure as a function of reaction time for the hydrogenolysis of methyl benzoate using various Ru catalysts with and without the use of acid from example 5.
Figure 2 is a graph of hydrogen pressure as a function of reaction time for hydrogenolysis of valerolactam using various Ru catalysts with and without the use of acid from example 6.
Detailed description of the invention
It has been surprisingly found that a coordination complex comprising ruthenium as a central metal and a ligand represented by structural formula (I):
Figure 370275DEST_PATH_IMAGE003
the coordination complexes are particularly effective as catalysts for the hydrogenolysis of amides to form amines and optionally alcohols.
Thus, in one aspect, the invention relates to compounds of formula (I).
The compound of formula (I) may be named "1, 1, 1-tris (bis (3, 5-dimethoxyphenyl) phosphinomethyl) ethane". It may also be referred to herein as "triphos- (OMe)2'OR' triphos (OMe)2”。
Triphos-(OMe)2Can be prepared by contacting bis (3, 5-dimethoxyphenyl) phosphine with tris (bromomethyl) ethane in a compatible solvent in the presence of a base. The solvent is not particularly limited as long as it can sufficiently dissolve the reactants and the base. Suitable solvents include polar aprotic solvents, such as dimethyl sulfoxide (DMSO). The base is also not particularly limited. Suitable bases include alkali metal alkoxides, such as potassium tert-butoxide. The reaction may be carried out at room temperature.
In another aspect, the present invention relates to organometallic compounds having the structural formula (II):
Figure 358959DEST_PATH_IMAGE004
wherein
Ar represents 3, 5-dimethoxyphenyl, and
l represents a leaving group.
The leaving group L represents one or more "volatile" or easily removable ligands that stabilize the complex so that it can be manipulated prior to the hydrogenolysis reaction, but is typically replaced by one or more reactants during the reaction sequence. Examples of such volatile ligands include trimethylene methane, allyl, methallyl, ethylene, cyclooctadiene, acetylacetonate, and acetate/salt/radical.
In various embodiments, the leaving group L comprises trimethylene methane. In this case, the organometallic compound has the structural formula (IIa):
Figure 907752DEST_PATH_IMAGE005
wherein Ar represents 3, 5-dimethoxyphenyl.
The compound of formula (IIa) may be referred to herein as "[ Ru (triphos- (OMe)2)TMM]"or" [ Ru (omphos)2)TMM]”。
The compound of formula (II) may be prepared by reacting triphos- (OMe)2With a Ru-containing compound.
The Ru-containing compound is not particularly limited. It may be a ruthenium-containing salt or complex, regardless of its formal oxidation state. Suitable Ru-containing compounds include Ru (acac)3[ Ru (COD) (methallyl)2]Ru (NBD) (methallyl)2Ru (ethylene)2(methallyl)2、[(COD)RuCl2]n、RuCl3、[(PPh3)3Ru(H)(CO)CI]And [ (cyclopentadienyl manganese tricarbonyl) RuCI2]2（[(cymanthren)RuCl2]2）。
In various embodiments, the Ru-containing compound comprises [ Ru (COD) (methallyl)2]。
The reaction to form the compound of formula (II) may be carried out at room temperature or at elevated temperature, for example 60 to 210 ℃, 100 to 200 ℃, or 120 to 180 ℃.
As mentioned above, comprising ruthenium and triphos- (OMe)2The complexes of (a) are particularly effective as catalysts for the hydrogenolysis of amides to form amines and optionally alcohols.
Thus, in another aspect, the present invention provides a process for the hydrogenolysis of an amide. The method comprises the following steps:
contacting the amide with hydrogen in the presence of an organometallic catalyst comprising a central metal and a tridentate ligand under conditions effective to form an amine and optionally an alcohol,
wherein the central metal comprises ruthenium, and
wherein the tridentate ligand has the structural formula (I) herein.
It should be noted that not all phosphines have to be combined with ruthenium during the reaction. In addition, not all phosphorus atoms may catalytically participate in the reaction.
The amount of organometallic catalyst used to carry out the reaction can vary within wide limits. For example, the catalyst concentration may be in the range of 0.01 to 10 mole percent based on the initial amount of amide.
The hydrogenolysis process can be carried out without the addition of an acid.
Alternatively, the hydrogenolysis process can be carried out in the presence of an acid.
Thus, in yet another aspect, the present invention provides a catalyst composition comprising a compound having structural formula (II) or (IIa) and an acid.
In the case where one or more acids are used in the hydrogenolysis reaction, the (initial) concentration of the acid may be 0.5 to 20 times the ruthenium concentration (on a molar basis). Other acid concentrations include 0.8 to 10 times, 1 to 5 times, or 1 to 2 times the ruthenium concentration (on a molar basis).
The acid is not particularly limited. For example, it may be organic or inorganic, such as sulfonic acids, especially methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and sulfuric acid; trifluoroacetic acid; perchloric acid; and mixtures thereof. Other suitable acids include those that provide weakly coordinating anions upon deprotonation, such as bis (trifluoromethane) sulfonimide (HNTf)2) Or mixtures thereof with the above acids.
In various embodiments, the acid can be HNTf2Methanesulfonic acid (MSA), tris (pentafluorophenyl) borane (B (C)6F5)3) Or aluminum trifluoromethanesulfonate (Al (OTf)3)。
The temperature used to carry out the hydrogenolysis contacting step can vary over a wide range. For example, it may be carried out at room temperature up to, for example, 250 ℃. Other contacting step temperatures include 60 to 210 ℃, 120 to 200 ℃, and 140 to 180 ℃.
Depending on the amide to be reacted, the process can be carried out in the absence or presence of an added solvent. The solvent may be a conventional non-polar solvent, such as an aliphatic or aromatic hydrocarbon, or a weakly polar, aprotic solvent, such as an ether. Examples of the aliphatic solvent include pentanes and hexanes. Examples of aromatic solvents include benzene, xylenes, toluene, and trimethylbenzenes. Examples of ethers include tetrahydrofuran, dioxane, diethyl ether, and polyethers.
The contacting step may be carried out at an initial hydrogen pressure of at least 1 bar, at least 10 bar, or at least 20 bar, and in each case at most 1000 bar, at most 750 bar, at most 500 bar, at most 250 bar, or at most 100 bar.
There is no particular limitation on the type of amide that may be converted in the hydrogenolysis process of the present invention. For example, the amide may be a primary, secondary, or tertiary amide, although a primary amide may be less selectively reduced than a secondary or tertiary amide. In various embodiments, the amide is a secondary or tertiary amide. Specific examples of amides which can be used in the process of the present invention include N-methylacetamide, N-dimethylacetamide, N-methylpropionamide, N-dimethylpropionamide, N-methylisobutylamide, N-dimethylisobutyramide, N-methylbutanamide, N-dimethylbutanamide, N-methylpentanamide, N-dimethylpentanamide, N-methylhexanamide, N-dimethylhexanamide, N-methylbenzamide, N-dimethylbenzamide, N-methylbenzacetamide, N-dimethylbenzacetamide, 2-ethyl-N-methylhexanamide, 2-ethyl-N, N-dimethylhexanamide, N-methyldecanamide, n, N-dimethyldecanamide, N-hexylhexanamide, N-acetylpyrrolidine, N-acetylpiperidine, N-acetylmorpholine, N-benzyl-2-methoxyacetamide, N-methylhydroxyacetamide, N-dimethylhydroxyacetamide, N-hexyl-2-methoxyacetamide, N-hexyl-3-methyloxetane-3-carboxamide, N-hexyl-2-furylcarboxamide, N-benzylbenzamide, N-ethylacetamide, N-methylpropionamide, N-cyclohexyl-2-methoxyacetamide, N-phenylacetamide, N-phenylhexanamide, 2-methoxy-N-phenylacetamide, N-hexylamide, N-hexylformamide, N-cyclohexylacetamide, N-cyclohexylformamide, N-phenylacetamide, N-cyclohexylformamide, N-phenylformamide, N-cyclohexylamide, N-hexylformamide, N-phenylbenzamide, ethylenediamine-N, N '- (2-methoxyacetamide), N-hexanoylmorpholine, N-butyrylmorpholine, N-2-methoxyacetylpyrrolidine, N-formylmorpholine, N, N-dimethylformamide, N, N-dimethylbenzamide, tetramethyloxamide, N, N, N', N '-tetramethyl-1, 4-cyclohexanedicarboxamide and N, N' -dimethyl-1, 4-cyclohexanedicarboxamide.
The process of the invention may also be used for hydrogenolysis of cyclic amides such as chi-butyrolactam, -valerolactam, -caprolactam, piperazin-2-one, cyclodiglycine, cycloglycyl-L-valine, N-methylpyrrolidone, N-phenylpyrrolidone, N-ethyl-pyrrolidone, N-butylpyrrolidone, N-methylpiperidinone, N-methyl-5-methylpiperidinone, N-methylcaprolactam and N-ethylcaprolactam.
In various embodiments, the amide is-valerolactam, N-hexylhexanamide, N-methyldecanoamide, or N-dimethyldecanoamide.
To the extent any doubt, the invention includes and explicitly contemplates and discloses any and all combinations of embodiments, features, characteristics, parameters and/or ranges mentioned herein. That is, the inventive subject matter may be defined by any combination of embodiments, features, characteristics, parameters, and/or ranges mentioned herein.
It is contemplated that any ingredient, component, or step that is not specifically named or identified as part of the present invention can be explicitly excluded.
Any process/method, apparatus, compound, composition, embodiment, or component of the present invention can be modified by transitional terms "comprising," "consisting essentially of," or "consisting of," or variations of these terms.
As used herein, the indefinite articles "a" and "an" mean one or more, unless the context clearly dictates otherwise. Similarly, the singular form of a noun includes the plural form thereof, and vice versa, unless the context clearly dictates otherwise.
Notwithstanding that accuracy has been attempted, the values and ranges set forth herein should be considered as approximations. These values and ranges can vary from their stated values depending on the desired properties desired to be obtained by the present disclosure, as well as variations resulting from the standard deviations found in measurement techniques. Moreover, the ranges set forth herein are intended to, and are specifically intended to, include all sub-ranges and values within the stated ranges. For example, a range of 50 to 100 is intended to include all values within the range, including sub-ranges such as 60 to 90, 70 to 80, and the like.
Any two numbers of the same property or parameter reported in the working examples may define a range. Those numbers may be rounded to the nearest thousandth, hundredth, tenth, integer, ten, hundred or thousand to define the range.
The contents of all documents, including patent and non-patent documents, cited herein are hereby incorporated by reference in their entirety. The disclosure herein should take precedence over any incorporated subject matter to the extent it conflicts with any disclosure herein.
The invention is further illustrated by the following working examples, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
Examples
Example 1
Synthesis of bis (3, 5-dimethoxyphenyl) phosphine oxide
Figure 464636DEST_PATH_IMAGE006
Magnesium oxide turnings (3.2 g, 0.138 mmol, 1.2 equiv.) were weighed into a 500 mL three-necked round bottom flask. 2-MTHF (2-methyltetrahydrofuran) (100 mL) was added and a small amount of I was added2Added to the stirred suspension. 1-bromo-3, 5-dimethoxybenzene (25 g, 0.115 mmol, 1 eq) was diluted in 2-MTHF (60 mL) and added to the vigorously stirred reaction suspension via the dropping funnel. When the Grignard reaction started (exothermic reaction and color change of the reaction suspension from colorless to pale yellow), the reaction flask was placed in a pre-heated oil bath at 70 ℃. 1-bromo-3, 5-dimethoxybenzene solution was added over 3 hours. After the addition was complete, the resulting orange solution was cooled to 0 ℃ with an ice bath and diethyl phosphite (5.24 g, 0.038 mmol, 0.33 eq.) diluted in 2-MTHF (60 mL) was added over 2 hours via a dropping funnel. The reaction solution was allowed to heat overnight before quenching with semi-concentrated (half concentrated) aqueous HCl (50 mL). By H2The organic layer was washed with O (2X 50 mL) and saturated saline solution (50 mL). The resulting pale yellow gel was suspended in Et2O and M t BE, and the product was obtained in the form of a white powder.
Yield: 5.6g, 50% by weight1H、13C and31the purity by P-NMR spectroscopy was 98%.
Example 2
Synthesis of bis (3, 5-dimethoxyphenyl) phosphine
Figure 466090DEST_PATH_IMAGE007
Bis (3, 5-dimethoxyphenyl) phosphine oxide (5.6 g, 0.017 mmol, 1 eq) was dissolved in a mixture of 2-MTHF (40 ml) and THF (20 ml) in a 100 ml Schlenk tube. A solution of DIBAL-H (3.6 g, 0.025 mmol, 1.5 equiv.) in 2-MTHF (20 ml) was added dropwiseInto a vigorously stirred reaction solution. (Note H)2Let out). Once the addition was complete, the reaction was allowed to stir at room temperature for 2 hours. Then, 1M aqueous NaOH (4 ml) and H were added2The reaction was quenched with O (20 ml). Since the quenched reaction solution became a gel without phase separation, acetic acid (5 mL) was added to the gel. After stirring for 5 minutes, the reaction solution was allowed to settle. Subsequently, the organic phase was separated and the solvent was removed in vacuo. The product was purified by distillation at 190 ℃ in high vacuum (0.001 mbar) and obtained as colorless oil which crystallized as a colorless solid overnight.
Yield: 2.7g, 49% by weight1H，13C and31the purity by P-NMR spectroscopy was 98%.
Example 3
Triphos-(OMe)2Synthesis of (2)
Figure 9198DEST_PATH_IMAGE008
In a 100 ml Schlenk tube, bis (3, 5-dimethoxyphenyl) phosphine (1 g, 3.26 mmol, 3.2 equiv.) and potassium tert-butoxide (386.8 mg, 3.45 mmol, 3.4 equiv.) were dissolved in DMSO (8 ml). The clear, pale red solution was stirred at room temperature for 1 hour, then a solution of 1,1, 1-tris (bromomethyl) ethane (314 mg, 1.02 mmol, 1 eq.) in DMSO (3 mL) was added dropwise. The reaction was stirred at room temperature for 16 hours. Subsequently, with H2The reaction was quenched with O (40 mL). Separating the white solid gel and using MtBE (3X 20 ml) extracted the milky aqueous solution. The white gel and organic phases were combined and dried under high vacuum. The resulting gel was purified in boiling EtOH (20 ml) and obtained as a colorless gel.
Yield: 778 mg, 78% by1H、13C and31the purity of the P-NMR-spectroscopy is > 99%.
Example 4
[Ru (triphos-(OMe)2) Synthesis of TMM
Figure 412497DEST_PATH_IMAGE009
Will triphos- (OMe)2(440 mg, 0.477 mmol, 1 eq.) and [ Ru (COD) (methallyl)2](142.7 mg, 0.477 mmol, 1 eq.) was weighed into a 45 ml Schlenk tube and dissolved in mesitylene (10 ml). The reaction was stirred at 130 ℃ for 16 hours, whereby the product precipitated from the reddish reaction solution. The precipitate was separated, washed with pentane (2 × 10 mL), and dissolved in DCM (dichloromethane) (3 mL). The clear yellow solution was dried under vacuum at 80 ℃. The product was obtained in the form of a yellow powder.
Yield: 306 mg, 60% by weight1H、13C and31the purity by P-NMR-spectroscopy was 98%.
Example 5
Hydrogenolysis of methyl benzoate
Figure 140282DEST_PATH_IMAGE010
Under the same reaction conditions (0.5 mol% [ catalyst ]]16 hours reaction time, 140 ℃, 2 ml, 1, 4-dioxane, 100 bar H2) Methyl benzoate is subjected to hydrogenolysis using three different catalysts, each with and without an acid, to form benzyl alcohol and methanol. The catalyst being [ Ru (triphos-xyl) TMM]、[Ru(triphos-(CF3)2)TMM]And [ Ru (triphos- (OMe)2)TMM]. The acid is HNTf2。
The results are shown in FIG. 1.
As can be seen from FIG. 1, the catalyst of the invention [ Ru (triphos- (OMe)2)TMM]Complete conversion was obtained both with and without acidic additives.
In the absence of HNTf2In the mean time, [ Ru (triphos- (OMe)2)TMM]With [ Ru (triphos-xyl) TMM]As fast.
In the presence of HNTf2In the mean time, [ Ru (triphos- (OMe)2)TMM]The ratio [ Ru (triphos-xyl) TMM]Slow.
Example 6
Hydrogenolysis of valerolactam
Figure 753666DEST_PATH_IMAGE011
Under the same reaction conditions (0.5 mol% [ catalyst ]]16 hours reaction time, 160 ℃, 2 ml of THF, 100 bar H2) The hydrogenolysis of valerolactam to form piperidine was carried out using three different catalysts, each with and without an acid. The catalyst being [ Ru (triphos-xyl) TMM]、[Ru(triphos-(CF3)2)TMM]And [ Ru (triphos- (OMe)2)TMM]. The acid is methanesulfonic acid.
The results are shown in FIG. 2.
As can be seen from FIG. 2, the catalyst of the invention [ Ru (triphos- (OMe)2)TMM]Complete conversion was obtained in both the presence and absence of methanesulfonic acid. The reaction rate is related to the [ Ru (triphos-xyl) TMM]The reaction rate of (A) is comparable.
Additional observations can be made by comparing the data in fig. 1 with the data in fig. 2. Figure 1 shows that the rate of hydrogenolysis from methyl benzoate to benzyl alcohol catalysed by a triphos derivative having methyl groups in the 3-and 5-positions of the aromatic group is substantially the same as the rate of hydrogenolysis catalysed by a triphos derivative having methoxy groups in the 3-and 5-positions (in the absence of an acid co-catalyst (co-catalyst)). However, when a strong-noncoordinating acid, such as triflic acid (HNTf), is added to the reaction mixture2) The use of the dimethyl substituted catalyst is much faster than hydrogenolysis using the 3, 5-dimethoxy substituted catalyst. In contrast, for the cyclic amide substrate valerolactone (fig. 2), although the hydrogenolysis rates of the 3, 5-dimethyl and 3, 5-dimethoxytriphos derivative catalysts were similar in the absence of the acid co-catalyst, both were accelerated to very similar extents by the presence of methanesulfonic acid (MSA). Thus, 3, 5-dimethoxyphenyl triphos derivatives, together with an acid co-catalyst, are excellent catalysts for the hydrogenolysis of amides.
Example 7
Hydrogenolysis of N-hexylhexanamide
Figure 225098DEST_PATH_IMAGE012
Under the same reaction conditions (0.5 mmol [ substrate ]]10. mu. mol of [ catalyst ]]10 μmol [ acid ]]16 hours reaction time, 160 ℃, 2 ml of THF, 100 bar H2) The hydrogenolysis of N-hexylhexanamide was carried out using two different catalysts, each using two different acids. The catalysts, acids and results are reported in table 1.
TABLE 1
Catalyst (2 mol%) Acid (2 mol%) Hexylamine (%) Hexanol (%) Dihexylamine (%) Trihexylamine (%) Conversion (%)
[Ru(triphos-xyl)TMM] B(C6F5)3 7.6 5.4 26.03 2.1 34.6
[Ru(triphos-(OMe)2)TMM] B(C6F5)3 - - 84.00 16.00 99.0
[Ru(triphos-xyl)TMM] Al(OTf)3 5.4 13.1 19.04 1.4 37.2
[Ru(triphos-(OMe)2)TMM] Al(OTf)3 4.3 12.5 25.2 5.6 35.1
Example 8
Hydrogenolysis of N-methyldecanoamides
Figure 482904DEST_PATH_IMAGE013
A1: 2 molar ratio of [ Ru (triphos-xyl (OMe) ]was used2)TMM]And Al (OTf)3For theNThe hydrogenolysis effect of the methyl decylamine is best. Thus, when at 160 ℃ and H2Use of [ Ru (triphos- (OMe) under (100 bar) atmosphere2)TMM](10. mu. mol) and 2 mol% of Al (OTf)3Make itNWhen (1.0 mmol) of methyl decyl amine was reacted, an amide conversion of 96% was observed. The reaction produced 16% decanol, 52% methyldecamine and 32% methyldodecylamine.
Example 9
Hydrogenolysis of N-dimethyldecanamide
Figure 647169DEST_PATH_IMAGE014
A1: 2 molar ratio of [ Ru (triphos- (OMe) was used2)TMM]And B (C)6F5)3For theN,N-The hydrogenolysis effect of the dimethyl decylamine is best. Thus, when at 160 ℃ and H2Use of [ Ru (triphos- (OMe) under (100 bar) atmosphere2)TMM](10. mu. mol) and 2 mol% B (C)6F5)3Make itN,N-When dimethyldecylamine (1.0 mmol) was reacted, 99% amide conversion was observed. The reaction yielded 3% decanol and 97% dimethyldecylamine.
The invention has been described in detail with particular reference to specific embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (15)

1. A compound having the structural formula (I):
Figure 128811DEST_PATH_IMAGE001
。
2. a process for preparing the compound of claim 1, comprising contacting bis (3, 5-dimethoxyphenyl) phosphine with 1,1, 1-tris (bromomethyl) ethane in the presence of a base.
3. An organometallic compound having the structural formula (II):
Figure 514793DEST_PATH_IMAGE002
wherein
Ar represents 3, 5-dimethoxyphenyl, and
l represents a ligand selected from the group consisting of trimethylene methane, allyl, methallyl, ethylene, cyclooctadiene, acetylacetonate and acetate/salt/radical.
4. The compound of claim 3, wherein L comprises trimethylene methane.
5. A process for preparing the organometallic compound of claim 3 comprising contacting a Ru-containing compound with a compound having the structural formula (I):
Figure 28951DEST_PATH_IMAGE003
。
6. the method of claim 5, wherein the Ru-containing compound is selected from the group consisting of Ru (acac)3[ Ru (COD) (methallyl)2]Ru (NBD) (methallyl)2Ru (ethylene)2(methallyl)2、[(COD)RuCl2]n、RuCl3、[(PPh3)3Ru(H)(CO)Cl]And [ (cyclopentadienyl manganese tricarbonyl) RuCl2]2。
7. The method of claim 6, wherein the Ru-containing compound comprises [ Ru (COD) (methallyl)2]。
8. A catalyst composition comprising the organometallic compound of claim 3 or 4 and an acid.
9. Catalyst set according to claim 8A compound wherein the acid is selected from HNTf2Methanesulfonic acid, B (C)6F5)3And Al (OTf)3。
10. A method for hydrogenolysis of an amide comprising:
contacting the amide with hydrogen in the presence of an organometallic catalyst comprising a central metal and a tridentate ligand under conditions effective to form an amine and optionally an alcohol,
wherein the central metal comprises ruthenium, and
wherein the tridentate ligand has structural formula (I):
Figure 33947DEST_PATH_IMAGE004
。
11. the method of claim 10, carried out in the absence of added acid.
12. The method of claim 10, which is carried out in the presence of an acid.
13. The method of claim 12, wherein the acid is selected from HNTf2Methanesulfonic acid, B (C)6F5)3And Al (OTf)3。
14. The method of any one of claims 10-13, wherein the catalyst comprises a compound having the structural formula (IIa):
Figure 582740DEST_PATH_IMAGE005
wherein Ar represents 3, 5-dimethoxyphenyl.
15. The method of any one of claims 10 to 14, wherein the amide comprises-valerolactam, N-hexylhexanamide, N-methyldecanoamide, or N-dimethyldecanoamide.
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